Polymerized oils &amp; methods of manufacturing the same

ABSTRACT

Described herein is a polymerized biorenewable, previously modified, or functionalized oil, comprising a polymeric distribution having about 2 to about 80 wt % oligomer content, a polydispersity index ranging from about 1.30 to about 2.20, and sulfur content ranging from 0.001 wt % to about 8 wt %. Methods of manufacturing the polymerized oil as well as its incorporation into asphalt paving, roofing, and coating applications are also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/227,866, filed Dec. 20, 2018, which is a continuation of U.S. patentapplication Ser. No. 15/715,665, filed Sep. 26, 2017 (U.S. Pat. No.10,316,189, issued Jun. 11, 2019), which is a divisional of U.S. patentapplication Ser. No. 15/553,643, filed Aug. 25, 2017, which is anational phase application of PCT Application No. PCT/US2016/019767,filed Feb. 26, 2016, which claims the benefit of U.S. ProvisionalApplication No. 62/126,064 filed Feb. 27, 2015, each of which isincorporated by reference herein in its entirety.

TECHNICAL FIELD

This disclosure relates to polymerized oils and methods for polymerizingoils and blending with asphalt to enhance performance of virgin asphaltand/or pavements containing recycled and aged bituminous material.

BACKGROUND

Recent technical challenges facing the asphalt industry have createdopportunities for the introduction of agriculture-based products for theoverall performance enhancement of asphalt. Such performanceenhancements may include expanding the useful temperature interval (UTI)of asphalt, rejuvenating aged asphalt, and compatibilizing elastomericthermoplastic polymers in asphalt.

SUMMARY

Aspects described herein provide a polymerized oil, comprising apolymeric distribution having about 2 to about 80 wt % oligomer content,a polydispersity index ranging from about 1.30 to about 2.20, and sulfurcontent ranging from 0.001 wt % to about 8 wt %.

Other aspects described herein provide a method of polymerizing an oilcomprising heating a biorenewable, previously modified, orfunctionalized oil to at least 100° C., adding a sulfur-containingcompound to the heated oil, and allowing the sulfur-containing compoundto react with the oil to produce a polymerized oil comprising apolymeric distribution having about 2 to about 80 wt % oligomer content,a polydispersity index ranging from about 1.30 to about 2.20, and sulfurcontent ranging from 0.001 wt % to about 8 wt %.

Yet other aspects described herein provide the incorporation of thepolymerized oil in asphalt paving, roofing, and coating applications.

DESCRIPTION OF THE FIGURES

FIGS. 1 and 2 show a complex modulus curve of asphalt as a function ofreduced loading frequency.

FIG. 3 illustrates a comparison of the DSC specific heat curves.

DETAILED DESCRIPTION

“Flash Point” or “Flash Point Temperature” is a measure of the minimumtemperature at which a material will initially flash with a brief flame.It is measured according to the method of ASTM D-92 using a ClevelandOpen Cup and is reported in degrees Celsius (° C.).

“Oligomer” is defined as a polymer having a number average molecularweight (Mn) larger than 1000. A monomer makes up everything else andincludes monoacylgyclerides (MAG), diacylglycerides (DAG),triacylglycerides (TAG), and free fatty acids (FFA).

“Performance Grade” (PG) is defined as the temperature interval forwhich a specific asphalt product is designed. For example, an asphaltproduct designed to accommodate a high temperature of 64° C. and a lowtemperature of −22° C. has a PG of 64-22. Performance Grade standardsare set by America Association of State Highway and TransportationOfficials (AASHTO) and the American Society for Testing Materials(ASTM).

“Polydispersity Index” (also known as “Molecular Weight Distribution”)is the ratio of weight average molecular weight (Mw) to number averagemolecular weight (Mn). The polydispersity data is collected using a GelPermeation Chromatography instrument equipped with a Waters 510 pump anda 410 differential refractometer. Samples are prepared at an approximate2% concentration in a THF solvent. A flow rate of 1 ml/minute and atemperature of 35° C. are used. The columns consist of a Phenogel 5micron linear/mixed Guard column, and 300×7.8 mm Phenogel 5 microncolumns (styrene-divinylbenzene copolymer) at 50, 100, 1000, and 10000Angstroms. Molecular weights were determined using the followingstandards:

Mult- Mono- Arcol Epoxidized Acclaim ranol Acclaim Standard oleinDiolein LHT 240 Trio-lein Soybean Oil 2200 3400 8200 Molecular 356 620707 878 950 2000 3000 8000 Weight (Daltons)

“Useful Temperature Interval” (UTI) is defined as the interval betweenthe highest temperature and lowest temperature for which a specificasphalt product is designed. For example, an asphalt product designed toaccommodate a high temperature of 64° C. and a low temperature of −22°C. has a UTI of 86. For road paving applications, the seasonal andgeographic extremes of temperature will determine the UTI for which anasphalt product must be designed. UTI of asphalt is determined by aseries of AASHTO and ASTM standard tests developed by the StrategicHighway Research Program (SHRP) also known as the “Performance Grading”(PG) specification.

Asphalt and Bituminous Materials

For the purpose of this invention asphalt, asphalt binder, and bitumenrefer to the binder phase of an asphalt pavement. Bituminous materialmay refer to a blend of asphalt binder and other material such asaggregate or filler. The binder used in this invention may be materialacquired from asphalt producing refineries, flux, refinery vacuum towerbottoms, pitch, and other residues of processing of vacuum towerbottoms, as well as oxidized and aged asphalt from recycled bituminousmaterial such as reclaimed asphalt pavement (RAP), and recycled asphaltshingles (RAS).

Starting Oil Material

Biorenewable oils may be used as the starting oil material. Biorenewableoils can include oils isolated from plants, animals, and algae.

Examples of plant-based oils may include but are not limited to soybeanoil, linseed oil, canola oil, rapeseed oil, castor oil, tall oil,cottonseed oil, sunflower oil, palm oil, peanut oil, safflower oil, cornoil, corn stillage oil, lecithin (phospholipids) and combinations andcrude streams thereof.

Examples of animal-based oils may include but are not limited to animalfat (e.g., lard, tallow) and lecithin (phospholipids), and combinationsand crude streams thereof.

Biorenewable oils can also include partially hydrogenated oils, oilswith conjugated bonds, and bodied oils wherein a heteroatom is notintroduced, for example but not limited to, diacylglycerides,monoacylglycerides, free fatty acids, alkyl esters of fatty acids (e.g.,methyl, ethyl, propyl, and butyl esters), diol and triol esters (e.g.,ethylene glycol, propylene glycol, butylene glycol, trimethylolpropane),and mixtures thereof. An example of biorenewable oils may be wastecooking oil or other used oils.

Previously modified or functionalized oils may also be used as thestarting oil material. Examples of previously modified oils are thosethat have been previously vulcanized or polymerized by otherpolymerizing technologies, such as maleic anhydride or acrylic acidmodified, hydrogenated, dicyclopentadiene modified, conjugated viareaction with iodine, interesterified, or processed to modify acidvalue, hydroxyl number, or other properties. Some examples of previouslymodified oils are polyol esters, for example polyglycerol ester or acastor oil ester, or estolides. Such modified oils can be blended withunmodified plant-based oils or animal-based oils, fatty acids, glycerin,and/or lecithin. Examples of functionalized oils are those wherein aheteroatom (oxygen, nitrogen, sulfur, and phosphorus) has beenintroduced.

In preferred aspects, the starting oil material is recovered corn oil(typically residual liquids resulting from the manufacturing process ofturning corn into ethanol) (also known as “corn stillage oil”) or otherlow cost waste oils. In another preferred aspect, the starting oilmaterial comprises free fatty acids. One skilled in the art willrecognize that if higher functionality is desired, plant-based oilshaving higher levels of unsaturation may be used.

Sulfur Crosslinking of the Oil

In the various aspects, polymerization of the biorenewable, previouslymodified, or functionalized oil is achieved through crosslinking of thefatty acid chains and/or the glyceride fraction of the tri-glyceridemolecules contained in the biorenewable, previously modified, orfunctionalized oil utilizing a sulfur-containing compound. The sulfur inthe sulfur-containing compound is preferably in a reduced form. Thepolymerization method comprises the steps of (a) heating a biorenewable,previously modified, or functionalized oil (b) adding asulfur-containing compound to the heated oil, and (c) allowing thesulfur-containing compound to react with the oil to produce apolymerized oil with a desired polymeric distribution (having about 2 wt% to about 80 wt % oligomer content), polydispersity index (from about1.30 to about 2.20), and sulfur content (between about 0.01 wt % andabout 8 wt %).

In a first step, the biorenewable, previously modified, orfunctionalized oil is heated in a vessel equipped with an agitator to atleast 100° C. In more preferred aspects, the biorenewable, previouslymodified, or functionalized oil (may also be collectively referred toherein as the “oil”) is heated to at least 115° C. In preferred aspects,the sulfur-containing compound is gradually added to the heatedbiorenewable, previously modified, or functionalized oil and may beadded in either a solid or a molten form, however it shall be understoodthat the sulfur-containing compound may be added before the oil orsimultaneously with the oil. In preferable aspects, thesulfur-containing compound may be elemental sulfur, but is not limitedto such. The reaction between the sulfur and oil inherently increasesthe temperature of the oil-sulfur mixture and in preferred aspects, thereaction is held at temperatures between about 130° C. and about 250°C., more preferably between about 130° C. and about 220° C., and evenmore preferably between about 160° C. and about 200° C. during thecourse of the reaction.

The oil-sulfur mixture may be continuously sparged with a gas-containingstream during the polymerization reaction between the oil and thesulfur. The gas-containing stream may be selected from the groupconsisting of nitrogen, air, and other gases. The gas-containing streammay help facilitate the reaction and may also assist in reducing odors(H₂S and other sulfides) associated with the reaction, in the finalproduct. Use of air can be beneficial, as it may lead tooxi-polymerization of the oil in addition to the sulfurization process.

Optionally, accelerators may be used to increase the rate of thereaction. Examples of accelerators include, but are not limited to, zincoxide, magnesium oxide, dithiocarbamates.

The reaction may continue and may be continuously monitored using gelpermeation chromatography (GPC) and/or viscosity until the desireddegree of polymerization is achieved as discussed below.

The robustness of the sulfur crosslinking reaction and the ability touse it for the polymerization of lower cost feedstocks containing a highfree fatty acid content and residual moisture is an advantage of thispolymerization method compared to other processes, providing flexibilityin starting material selection.

Polymerization Characteristics

The reaction between the sulfur-containing compound and thebiorenewable, previously modified, or functionalized oil is driven untila polymeric distribution having between about 2 wt % and about 80 wt %oligomers (20 wt % to 98 wt % monomers), and more preferably betweenabout 15 wt % to about 60 wt % oligomers (40 wt % to 85 wt % monomers),and even more preferably between about 20 wt % to about 60 wt %oligomers (40 wt % to 80 wt % monomers) is achieved. In even morepreferred aspects, the polymeric distribution ranges from about 50 wt %to about 75 wt % oligomers and about 25 wt % to about 50 wt % monomers.

The polydispersity index of the polymerized oil ranges from about 1.30to about 2.20, and more preferably from about 1.50 to about 2.05.

A benefit of the reaction described herein is the low sulfur content inthe resulting polymerized oil. In some aspects, the sulfur content makesup less than 8 wt % of the polymerized oil. In other aspects, the sulfurcontent makes up less than 6 wt % of the polymerized oil. In yet otheraspects, the sulfur content makes up less than 4 wt % of the polymerizedoil. And in other aspects, the sulfur content makes up less than 2 wt %of the polymerized oil. The sulfur content, however, comprises at least0.001 wt % of the polymerized oil.

The flash point of the resulting polymerized oil, as measured using theCleveland Open Cup method, is at least about 100° C. and no more thanabout 400° C. In some aspects, the flash point of the polymerized oil isbetween about 200° C. and about 350° C. In other aspects, the flashpoint of the polymerized oil is between about 220° C. and about 300° C.In yet other aspects, the flash point of the polymerized oil is betweenabout 245° C. and about 275° C. The polymerized oils described hereinmay have higher flash point than its starting oil material, especiallywhen compared against other polymerization techniques.

The viscosity of the polymerized oil will vary based on the type ofstarting oil material, but generally ranges from about 1 cSt to about100 cSt at 100° C.

End-Use Applications

In one aspect, the present invention provides a modified asphaltcomprising a blend of 60 wt % to 99.9 wt % of asphalt binder and 0.1 wt% to 40 wt % of the polymerized oil, and a method for making the same,in which polymerization of the oil is achieved through sulfurcross-linking as described above. The modified asphalt may be used forroad paving or roofing applications.

In another aspect, the present invention provides a modified asphaltcomprising a blend of 60 wt % to 99.9 wt % asphalt binder and 0.1 wt %to 40 wt % of the polymerized oil, and a method for making the same,wherein the polymerized oil is a blend of an polymerized oil achievedthrough sulfur cross-linking, as described above, and one or more of thebiorenewable, previously modified or functionalized oils describedabove, for example: unmodified plant-based oil, animal-based oil, fattyacids, fatty acid methyl esters, gums or lecithin, and gums or lecithinin modified oil or other oil or fatty acid.

Other components, in addition to the polymerized oil, may be combinedwith an asphalt binder to produce a modified asphalt, for example butnot limited to, thermoplastic elastomeric and plastomeric polymers(styrene-butadiene-styrene, ethylene vinyl-acetate, functionalizedpolyolefins, etc.), polyphosphoric acid, anti-stripping additives(amine-based, phosphate-based, etc.), warm mix additives, emulsifiersand/or fibers. Typically, these components are added to the asphaltbinder/polymerized oil at doses ranging from about 0.1 wt % to about 10wt %.

Asphalt Modification

The declining quality of bitumen drives the need for adding chemicalmodifiers to enhance the quality of asphalt products. Heavy mineral oilsfrom petroleum refining are the most commonly used modifiers. Thesemineral oils extend the low temperature limit of the asphalt product by‘plasticizing’ the binder, however this also tends to lower the uppertemperature limit of the asphalt.

Mineral flux oils, petroleum-based crude distillates, and re-refinedmineral oils have been used in attempts to soften the asphalt. Often,use of such material results in a decrease of the high temperaturemodulus of asphalt more than the low temperature, making the asphaltmore prone to rutting at high temperatures. Such effects result in thereduction of the Useful Temperature Interval (UTI).

Mineral flux oils, petroleum-based crude distillates, and re-refinedmineral oils often have volatile fractions at pavement constructiontemperatures (e.g., 150 to 180° C.), generally have lower flashpointsthan that of asphalt, and may be prone to higher loss of performance dueto oxidative aging.

The polymerized oils and blends described herein are not only viablesubstitutes for mineral oil, but have also been shown to extend the UTIof asphalts to a greater degree than other performance modifiers,therefore providing substantial value to asphalt manufacturers. Theobserved increase in UTI using the polymerized oils described herein isa unique property not seen in other asphalt softening additives such asasphalt flux, fuel oils, or flush oils. Typically one grade improvementin either the SHRP Performance Grading (PG) specification or thePenetration grading system used in many countries is achieved withapproximately 2 to 3 wt % of the polymerized oil by weight of theasphalt. For example, the increase in UTI seen for approximately 3% byweight addition of the polymerized oil can be as much as 4° C.,therefore providing a broader PG modification range such that the lowerend temperature can be lower without sacrificing the higher endtemperature.

Rejuvenation of Aged Bituminous Material

Asphalt “ages” through a combination of mechanisms, mainly oxidation andvolatilization. Aging increases asphalt modulus, decreases viscousdissipation and stress relaxation, and increases brittleness at lowerperformance temperatures. As a result, the asphalt becomes moresusceptible to cracking and damage accumulation. The increasing usage ofrecycled and reclaimed bituminous materials which contain highly agedasphalt binder from sources such as reclaimed asphalt pavements (RAP)and recycled asphalt shingles (RAS) have created a necessity for“rejuvenators” capable of partially or completely restoring therheological and fracture properties of the aged asphalt. Aging ofasphalt has also been shown to increase colloidal instability and phaseincompatibility, by increasing the content of high molecular weight andhighly polar insoluble “asphaltene” fraction which may increasinglyassociate. The use of the polymerized oil described herein areparticularly useful for RAP and RAS applications. The polymerized oildescribed in this document act as a compatibilizer of the asphaltfractions, especially in aged and oxidized asphalt, resulting in abalanced and stable asphalt binder with restored performance anddurability.

During plant production the asphalt is exposed to high temperatures(usually between 150 to 190° C.) and exposure to air during whichsignificant oxidation and volatilization of lighter fractions can occurleading to an increase in modulus and a decrease in viscous behavior.The aging process is simulated using a Rolling Thin Film Oven (ASTMD2872) during which a rolling thin film of asphalt is subjected a jet ofheated air at about 163° C. for about 85 minutes. The rheologicalproperties are measured before and after the aging procedure using aDynamic Shear Rheometer following ASTM D7175 using the ratio of the|G*|/sin δ after to before aging, in which G* is the complex modulus andS is the phase angle. The larger the ratio of the (|G*|/sin δ) afteraging to the (|G*|/sin δ) before aging, the higher the effect ofoxidative aging and volatilization on the tested asphalt.

Using this procedure it is shown that asphalts treated with thepolymerized oil or blends thereof described in this invention have alower ratio, thus showing a lower tendency for change in rheologicalproperties as a result of oxidative aging and volatilization.

Accordingly, the polymerized oils described herein have been shown to becapable of rejuvenating aged asphalt binder, and modify the rheologicalproperties of a lesser aged asphalt binder. As a result, small dosagesof the polymerized oil can be used to incorporate high content of agedrecycled asphalt material into pavements and other applicationsresulting in significant economic saving and possible reduction in theenvironmental impact of the pavement through reduction of use of freshresources.

Elastomeric Thermoplastic Polymer Compatibilization in Asphalt

Asphalt is often modified with thermoplastic elastomeric and plastomericpolymers such as Styrene-Butadiene-Styrene (SBS) to increase hightemperature modulus and elasticity, to increase resistance to heavytraffic loading and toughening the asphalt matrix against damageaccumulation through repetitive loading. Such polymers are usually usedat 3 to 7 wt % dosages in the asphalt and high shear blended intoasphalt at temperatures exceeding 180° C. and allowed to “cure” atsimilar temperatures during which the polymer swells by adsorption oflighter fractions in the asphalt until a continuous volume phase isachieved in the asphalt.

The volume phase of the fully cured polymer will be affected by degreeof compatibility of the polymer in the asphalt and the fineness of thedispersed particles, resulting in an increased specific area andenhanced swelling potential through increase of the interface surfacebetween asphalt and polymer.

The polymerized oils described in this document have been shown to becapable of further compatibilizing elastomeric polymer in the asphalt,when the oil is added and blended into the asphalt before theincorporation of the polymer, or the curing stage. This will beespecially effective in asphalt binders that are not very compatiblewith the elastomeric polymer. Furthermore, the oil may contribute to thelighter fractions that swell the polymers during the curing period.

Warm Mix Additives and Asphalt

In recent years an increasing portion of pavements are produced usingwhat is commonly referred to as “warm mix additives” to produce “warmmix” asphalt pavements. Warm mix pavements can be produced and compactedat lower production temperatures, require less compaction effort toachieve target mixture density, and as a result can retain theproperties necessary for compaction at lower temperature enabling anincrease in the maximum haul distance of the asphalt mixture from theplant to the job site.

The different mechanisms through which warm mix additives provide abenefit include increased lubrication of aggregates during asphaltmixture compaction, reduction of the binder viscosity at productiontemperatures, and better coating and wettability of the aggregates. Thusa diverse range of chemicals and additives may exhibit one or more ofthe properties attributed to warm mix additives when added to an asphaltmixture.

The polymerized oils described herein can be used as a warm mix additiveand/or compaction aid, to achieve a number of the benefits expected froma warm mix additive, including minimum decreasing production andconstruction temperatures through increase in aggregate lubrication andaggregate wettability. In such an application the additive would be usedat dosages preferably in the range of between about 0.1 and 2% by weightof the bitumen.

EXAMPLES

The following examples are presented to illustrate the present inventionand to assist one of ordinary skill in making and using same. Theexamples are not intended in any way to otherwise limit the scope of theinvention.

Experimental Method

A charge of precipitated sulfur (mass ranges between 6.5 grams to 56.5grams) is added to a 1 liter round bottom flask containing 650 grams ofvegetable oil. The reactor is then heated to the target reactiontemperature using a heating mantle, taking care not to over shoot thetarget temperature by more than 5° C. The reaction mixture is agitatedusing a motorized stirrer with a stir shaft and blade. The reaction iscontinuously sparged with nitrogen at 2-12 standard cubic feet per hour(SCFH). A condenser and receiving flask is used to collect anydistillate.

It is noted that the reaction will create foam around 110-115° C. whenthe sulfur melts into the oil. The reaction is monitored using GPC, tomeasure the oligomer content and distribution, and viscosity is measuredat 40° C. using ASTM D445. The reaction is considered complete when thedesired oligomer content has been achieved. The reactor is then cooledto 60° C.

Example 1: Asphalt Modified with Polymerized Palm Oil #1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat (i.e., unmodified) asphalt binder graded        at a standard grade of PG64-22 (and “true” grade of PG        64.88-24.7) Note: the true grade represents the exact        temperatures at which the asphalt met the controlling        specification values, which will always meet and exceed that of        the corresponding standard grade (i.e. the true high temperature        grade will always be larger than the standard high temperature        grade, and the true low temperature grade will always be lower        than that of the standard low temperature grade).    -   3.0% by weight of sulfurized refined palm oil reacted with 3% by        weight of elemental sulfur at 160° C. for 5 hrs under a Nitrogen        sparge. This resulted in a modifier with:        -   31.8% oligomers        -   Viscosity of 17.2 cSt at 100° C.        -   Polydispersity Index (PDI) of approximately 1.30

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance with AASHTO M320. The modification resulted in a 4.8° C.low temperature grade improvement, taking the neat binder grade of PG64-22 to a PG 58-28. The net change in the high and low performancegrade resulted in a Useful Temperature Interval improved by 0.8° C.Details are shown Table 1.

TABLE 1 UTI¹ O-DSR² R-DSR³ S-BBR⁴ m-BBR⁵ Binder Name ° C. ° C. ° C. ° C.° C. Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized 90.4 60.0460.72 −30.4 −32.7 Refined Palm Oil #1 ¹UTI: Useful Temperature Interval,as the difference between the high temperature performance grade and thelow temperature performance grade, as determined using AASHTO M320.²O-DSR: The High Temperature Performance Grade of the Unaged(“Original”) asphalt binder as measured using a Dynamic Shear Rheometer(DSR) following ASTM D7175 and AASHTO M320. ³R-DSR: The High TemperaturePerformance Grade of the Rolling Thin Film Oven Aged (RTFO, followingASTM D2872) asphalt binder as measured using a Dynamic Shear Rheometer(DSR) following ASTM D7175 and AASHTO M320. ⁴S-BBR: The Low TemperaturePerformance Grade controlled by the Creep Stiffness parameter (“S”), asmeasured on an asphalt binder conditioned using both the Rolling ThinFilm Oven (ASTM D2872) and Pressure Aging Vessel (ASTM D6521), using aBending Beam Rheometer following ASTM D6648 and AASHTO M320. ⁵m-BBR: TheLow Temperature Performance Grade controlled by the Creep Rate parameter(“m” value), as measured on an asphalt binder conditioned using both theRolling Thin Film Oven (ASTM D2872) and Pressure Aging Vessel (ASTMD6521), using a Bending Beam Rheometer following ASTM D6648 and AASHTOM320.

Example 2: Asphalt Modified with Polymerized Palm Oil #2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of sulfurized refined palm oil reacted with 4% by        weight of elemental sulfur at 160° C. for 20.5 hrs under a        Nitrogen sparge. This resulted in a modifier with:        -   56.18% oligomers        -   Viscosity of 25.0 cSt at 100° C.        -   PDI of approximately 1.50

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5.9° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 1.5° C. Detailsare shown in Table 2.

TABLE 2 O-DSR |R-DSR UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. °C. ° C. ° C. Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% SulfurizedRefined 91.1 60.54 61.13 −30.6 −34.1 Palm Oil #2

Example 3: Asphalt Modified with Sulfurized Recovered Corn Oil #1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of sulfurized recovered corn oil (RCO) reacted        with 1.5% by weight of elemental sulfur at 160° C. for 7 hrs        under a Nitrogen sparge. This resulted in a modifier with:        -   16.0% oligomers        -   PDI of approximately 1.50

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 6.0° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 0.4° C. Detailsare shown in Table 3.

TABLE 3 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized RCO 1 90.0 59.2860.34 −30.7 −33.6

Example 4: Asphalt Modified with Sulfurized Recovered Corn Oil #2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of sulfurized recovered corn oil (RCO) reacted        with 6.0% by weight of elemental sulfur at 160° C. for 6 hrs        under a Nitrogen sparge. This resulted in a modifier with:        -   50.3% oligomers        -   Viscosity at 40° C. was 270 cSt        -   PDI of approximately 2.19

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 4.4° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 0.7° C. Detailsare shown in Table 4.

TABLE 4 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized RCO 90.3 61.2361.3  −29.1 −30.9 2

Example 5: Asphalt Modified with Sulfurized Refined Sunflower Oil Blend#1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   14.5% by weight of a sulfurized refined sun flower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   85.5% by weight of refined sunflower oil        -   Blend of the sulfurized oil and the unmodified oil had 11.9%            oligomer content, a viscosity of 55 cSt at 40° C., and a PDI            of approximately 1.64.

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5.3° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a full low temperature grade improvement with no change inthe Useful Temperature Interval. Details are shown in Table 5.

TABLE 5 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Sun 89.6 59.5560.40 −30.0 −30.3 Flower Oil Blend 1

Example 6: Asphalt Modified with Sulfurized Refined Sunflower Oil Blend#2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   53.9% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   46.1% by weight of refined sunflower oil        -   Blend of the sulfurized oil and the unmodified oil had            42.76% oligomer content, a viscosity of 177 Cst at 40° C.,            and a PDI of approximately 3.16.

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. The modification resulted in a 4.8° C.low temperature grade improvement, taking the neat binder grade of PG64-22 to a PG 58-28. Performance grade tests were performed inaccordance to AASHTO M320. The net change in the high and lowperformance grade resulted in a Useful Temperature Interval improved by0.1° C. Details are shown in Table 6.

TABLE 6 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Sun 89.7 60.2461.25 −29.5 −34.2 Flower Oil Blend 2

Example 7: Asphalt Modified with Sulfurized Refined Sunflower Oil Blend#3

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   63.4% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   36.6% by weight of refined sunflower oil        -   Blend of the sulfurized oil and the unmodified oil had 48.3%            oligomer content, a viscosity of 254 Cst at 40° C., and a            PDI of approximately 3.55.

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval improved by 0.8° C. Detailsare shown in Table 7.

TABLE 5 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Sun 90.4 60.7061.64 −29.7 −34.7 Flower Oil Blend 3

Example 8: Asphalt Modified with Refined Sunflower Oil Blend with PalmOil #1

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   14.5% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomers        -   84.5% by weight of palm oil        -   Blend of the sulfurized oil and the palm oil had about 11.9%            oligomer content        -   PDI of approximately 1.77

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 5° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval slightly decreased by 0.2° C.Details are shown in Table 8.

TABLE 6 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized SFO-Palm 89.459.65 60.58 −29.7 −30.1 Oil Blend 1

Example 9: Asphalt Modified with Sulfurized Refined Sunflower Oil Blendwith Palm Oil #2

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   3.0% by weight of a blend having:        -   59.0% by weight of a sulfurized refined sunflower oil            reacted with 7.0% by weight of elemental sulfur at 160° C.            for 19 hrs under a Nitrogen sparge. This resulted in a            modifier with 70.8% oligomer        -   41.0% by weight of palm oil        -   Blend of the sulfurized oil and the palm oil had about 43%            oligomer content, and a PDI of approximately 2.37

The modifier was blended into the asphalt after the binder had beenannealed at 150° C. for 1 hour. Performance grade tests were performedin accordance to AASHTO M320. The modification resulted in a 4.2° C. lowtemperature grade improvement, taking the neat binder grade of PG 64-22to a PG 58-28. The net change in the high and low performance graderesulted in a Useful Temperature Interval slightly decreased by 0.1° C.Details are shown in Table 9.

TABLE 7 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized SFO-Palm 89.560.62 61.24 −28.9 −33.1 Oil Blend 2

Example 10: Asphalt Modified with Sulfurized Soy Acid Oil (Also Known as“Acidulated Sap Stock”)

A modified asphalt binder comprising:

-   -   97.0% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)

3.0% by weight of a sulfurized refined Soy Acid Oil reacted with 5.0% byweight of elemental sulfur at 160° C. for 8 hrs under a Nitrogen sparge.This resulted in a modifier with 28.14% oligomer, a viscosity of 167 cStat 40° C., and a PDI of approximately 2.36. The modifier was blendedinto the asphalt after the binder had been annealed at 150° C. for 1hour. Performance grade tests were performed in accordance to AASHTOM320. The modification resulted in a 3.3° C. low temperature gradeimprovement, taking the neat binder grade of PG 64-22 to a PG 58-28. Thenet change in the high and low performance grade resulted in a UsefulTemperature Interval decreased by 1.5° C. This example highlights thepotential undesirable effect of the free fatty acid content on themodifier's performance, as it is significantly less effective inimproving the low temperature performance grade compared to the dropcaused at the high temperature grade. Details are shown in Table 10.

TABLE 8 UTI O-DSR R-DSR S-BBR m-BBR Binder Name ° C. ° C. ° C. ° C. ° C.Unmodified 89.6 64.88 65.88 −25.8 −24.7 +3% Sulfurized Soy Acid 88.160.07 61.39 −28   −31.6 Oil

Example 11: Asphalt Modified with StyreneButadieneStyrene and SulfurizedRecovered Corn Oil #1 as a Compatabilizer

A modified asphalt binder comprising:

-   -   92.41% by weight of neat asphalt binder graded as PG64-22 (true        PG 64.88-24.7)    -   5.5% by weight of Linear StyreneButadieneStyrene (SBS)    -   0.09% by weight of Elemental Sulfur (used as an SBS cross linker        in the asphalt binder    -   2.0% by weight of sulfurized recovered corn oil (RCO) as        described in Example #3.

Blending Procedure:

-   -   1. The modifier was blended into the asphalt after the binder        had been annealed at 150° C. for 1 hour. The modified binder        heated to about 193° C. for polymer modification.    -   2. The RPM in the high shear mixer was set to 1000 while the SBS        was added (within 1 minute). Immediately after addition of the        polymer the RPM was briefly ramped up to 3000 rpm for        approximately 10 minutes to insure full break down of the SBS        pellets, after which the shear level was lowered to 1000 rpm.    -   3. Polymer blending was continued at 1000 rpm for a total of 2        hrs.    -   4. Temperature was dropped to about 182° C. at a 150 rpm at        which point the sulfur cross linker was added.    -   5. Blending was continued at 182° C. and 150 rpm for 2 hrs.    -   6. Polymerized binder was placed in an oven at 150° C. for        approximately 12-15 hrs (overnight) to achieve full swelling of        the polymer.

Performance grade tests were performed in accordance to AASHTO M320.Multiple Stress Creep and Recovery tests were performed on the unagedbinder at 76° C. and on the RTFO residue at 64° C. in accordance toAASHTO T350. The results show that despite the reduction in modulus theaverage percent of recovery of the binder increased for the bindercontaining the modifier, indicating the effect of the modifier as acompatibilizer of SBS, resulting in a better distribution of the samemass of the elastomeric polymer compared to the binder that did notcontain the modifier and consequently a more efficient elastic network.Details are shown in Table 11.

TABLE 9 MSCR at 3.2 kPa MSCR at 3.2 kPa DSR |G*|/sinδ Recovery at 64° C.Recovery at 76° C. Unaged (RTFO) (Unaged) Binder Name 70° C. 76° C. 82°C. (%) (%) +5.5% SBS + 0.09% Sulfur 4.05 2.51 1.62 89.0% 67.7% +2%Example#1 + 5.5% 3.34 2.11 1.40 93.1% 70.0% SBS + 0.09% Sulfur

Example 12: Rejuvenation of Highly Aged Asphalt Binder Using the Oil ofExample #3

The example shown in FIG. 1 shows a complex modulus (G*) curve ofasphalt as a function of reduced loading frequency, measured using aDynamic Shear Rheometer (DSR) following ASTM D7175. The measurementswere made for samples of the asphalt binder used in Example #3 (PG64-22)after laboratory aging to three levels:

-   -   Aging Level 1: 85 minutes of oxidative aging in Rolling Thin        Film Oven at 163° C. (following ASTM D2872).    -   Aging Level 2: Continued aging of samples after aging level 1 by        subjecting it to 20 hrs of oxidative aging at 2.1 MPa air        pressure at 100° C. using a Pressure Aging Vessel (following        ASTM D6521). According to the Performance Grading specification,        20 hrs of PAV aging accelerates the simulated aging that would        normally occur during the performance life of an asphalt        pavement.    -   Aging Level 3: Continued aging of samples after aging level 1        and 2 by subjecting it to an additional 20 hrs of oxidative        aging using a Pressure Aging Vessel (PAV) for a total of 40 hrs        of PAV aging, representing the aging level of a binder from a        severely aged pavement.

FIG. 1 shows that additional aging from level 1 to level 2, and level 2to level 3 caused significant increase in complex modulus across thereduced frequency spectrum.

The asphalt binder at Aging Level 3 was “rejuvenated” by heating thebinder to 150° C. for 1 hr and blending in 5% by weight of the totalbinder of the Example #3 oil. The curve corresponding to the rejuvenatedbinder in FIG. 1 shows that the rejuvenation significantly decreased theG* of the aged asphalt across the whole spectrum of reduced frequencies,resulting in a binder with the rheological properties of a significantlylower aged asphalt binder.

Example 13: Rejuvenation of Highly Aged Asphalt Binder Using the Oil ofExample #4

The example shown in FIG. 1 shows a complex modulus (G*) curve ofasphalt as a function of reduced loading frequency, measured using aDynamic Shear Rheometer (DSR) following ASTM D7175. The measurementswere made for samples of the asphalt binder used in Example #3 (PG64-22)after laboratory aging to three levels described in Example 12, asbefore, showing that additional aging caused significant increase incomplex modulus across the reduced frequency spectrum.

The asphalt binder at Aging Level 3 was “rejuvenated” by heating thebinder to 150° C. for 1 hr and blending in 5% by weight of the totalbinder of the Example #4 oil. The curve corresponding to the rejuvenatedbinder in FIG. 2 shows that the rejuvenation significantly decreased theG* of the aged asphalt across the whole spectrum of reduced frequencies,resulting in a binder with the rheological properties of a lower agedasphalt binder.

Example 14: Effect of Sulfurized Oil on Glass Transition

The low temperature performance of asphalt has been shown to besignificantly affected by the glass transition temperature of theasphalt, that will occur in the range of the performance temperatureoften experienced in the winter (approximately −5 to −40° C.).Furthermore, the rate of asphalt physical hardening has also been shownto be closely associated with glass transition of the asphalt, with thehighest rate occurring at the Tg. Thus it is desirable to have a lowglass transition temperature to reduce the likelihood that asphalt willreach its glass transition during its performance life. Aging has beenknown to increase the glass transition temperature of asphalt, thus adesirable attribute of an effective rejuvenator would be to lower theglass transition of the aged asphalt once incorporated.

The first measurement was made for a sample of a PG64-22 asphalt binderafter significant laboratory aging. The laboratory aging consisted of 85minutes of oxidative aging in Rolling Thin Film Oven at 163° C. (ASTMD2872) followed by 40 hrs of oxidative aging at 2.1 MPa air pressure at100° C. using a Pressure Aging Vessel (following ASTM D6521),representing the aging level of a binder from a severely aged pavement.The sample is labeled “Aged Asphalt” in FIG. 1 .

The second sample, labeled “Aged Asphalt+Polymerized Oil” consisted of:

-   -   95% by weight of the aforementioned PG58-28 neat binder    -   5% by weight of of sulfurized recovered corn oil (RCO) reacted        with 1.5% by weight of elemental sulfur at 160° C. for 7 hrs        under a Nitrogen sparge. This resulted in a modifier with 16.0%        oligomers and a PDI of approximately 1.50.

Thermal analysis of binders before and after rejuvenation using thepolymerized oil show that the modifier significantly shifted the Tg ofthe aged asphalt towards lower temperatures, as shown in Table 12. Acomparison of the DSC specific heat curves is shown in FIG. 3 .

TABLE 12 Glass Transition Temperature Material Description (° C.) AgedAsphalt −17 Aged Asphalt + Polymerized −27 Oil

1.-9. (canceled)
 10. The modified asphalt of claim 56, wherein thepolymerized oil is derived from a starting oil material selected fromthe group consisting of palm oil, sunflower oil, corn oil, soybean oil,canola oil, rapeseed oil, linseed oil, tung oil, castor oil, tall oil,cottonseed oil, peanut oil, safflower oil, corn stillage oil, andcombinations and crude streams thereof. 11.-13. (canceled)
 14. Themodified asphalt of claim 56, wherein the polymerized oil is derivedfrom a starting oil material selected from the group consisting oftriacyglycerides, diacylglycerides, monoacylglycerides, and combinationsthereof.
 15. The modified asphalt of claim 56, wherein the polymerizedoil is derived from a starting oil material comprising phospholipids.16. The modified asphalt of claim 56, wherein the polymerized oil isderived from a starting oil material comprising an animal fat.
 17. Themodified asphalt of claim 56, wherein the polymerized oil is derivedfrom a starting oil material comprising a vegetable oil.
 18. Themodified asphalt of claim 56, wherein the polymerized oil is derivedfrom a starting oil comprising free fatty acids.
 19. The modifiedasphalt of claim 56, wherein the polymerized oil is derived from astarting oil comprising a partially hydrogenated oil. 20.-37. (canceled)38. The modified asphalt of claim 56, wherein polymerized oil has asulfur content is less than about 6 wt %.
 39. The modified asphalt ofclaim 56, wherein the polymerized oil has a sulfur content is less thanabout 4 wt %.
 40. The modified asphalt of claim 56, wherein thepolymerized oil has a sulfur content is less than about 2 wt %. 41.-51.(canceled)
 52. The modified asphalt of claim 56, wherein the modifiedasphalt binder is for paving applications.
 53. The modified asphalt ofclaim 56, wherein the modified asphalt is for roofing applications. 54.The modified asphalt of claim 56, wherein the modified asphalt is forcoating applications.
 55. (canceled)
 56. A modified asphalt, comprising:(a) about 60 to about 99.9 wt % asphalt binder; and (b) about 0.1 toabout 40 wt % of a blend of polymerized oil crosslinked with asulfur-containing compound and unmodified biorenewable oil, previouslymodified or functionalized oil, wherein the polymerized oil has a i. apolymeric distribution having about 2 to about 80 wt % oligomer content;ii. a polydispersity index ranging from about 1.30 to about 2.20; andiii. sulfur content less than about 8 wt %.
 57. The modified asphalt ofclaim 56, further comprising at least one from the group consisting ofthermoplastic elastomeric and plastomeric polymers, polyphosphoric acid,anti-stripping additives, warm mix additives, emulsifier, and fibers.58.-64. (canceled)
 65. The modified asphalt of claim 56, furthercomprising reclaimed asphalt pavement millings.
 66. (canceled)
 67. Themodified asphalt of claim 56, wherein the unmodified biorenewable oilcomprises palm oil, sunflower oil, corn oil, soybean oil, canola oil,rapeseed oil, linseed oil, tung oil, castor oil, tall oil, cottonseedoil, peanut oil, safflower oil, corn stillage oil, lecithin(phospholipids) and combinations and crude streams thereof.